WO2016175605A1 - Séparateur pour un élément électrochimique présentant une meilleure mouillabilité d'électrolyte et élément électrochimique comprenant ce même séparateur - Google Patents

Séparateur pour un élément électrochimique présentant une meilleure mouillabilité d'électrolyte et élément électrochimique comprenant ce même séparateur Download PDF

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WO2016175605A1
WO2016175605A1 PCT/KR2016/004522 KR2016004522W WO2016175605A1 WO 2016175605 A1 WO2016175605 A1 WO 2016175605A1 KR 2016004522 W KR2016004522 W KR 2016004522W WO 2016175605 A1 WO2016175605 A1 WO 2016175605A1
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Prior art keywords
binder polymer
separator
solvent
lithium
inorganic particles
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PCT/KR2016/004522
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English (en)
Korean (ko)
Inventor
이주성
진선미
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020160052382A external-priority patent/KR102028113B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/548,185 priority Critical patent/US10581045B2/en
Publication of WO2016175605A1 publication Critical patent/WO2016175605A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator for an electrochemical device with improved electrolyte impregnation and an electrochemical device including the separator.
  • Electrochemical devices are the most attention in this respect, and among them, the development of a secondary battery capable of charging and discharging has become a focus of attention.
  • the electrochemical device has been developed by the continuous research, the electrode active material has improved a lot of performance, especially the output.
  • the secondary batteries currently applied lithium secondary batteries developed in the early 1990s have been in the spotlight for their advantages of higher operating voltage and higher energy density than conventional batteries such as Ni-MH.
  • electrochemical devices are produced by many companies, but their safety characteristics show different aspects. It is very important to evaluate the safety and secure the safety of these electrochemical devices. The most important consideration is that an electrochemical device should not injure the user in the event of a malfunction. For this purpose, safety standards strictly regulate the ignition and smoke in the electrochemical device.
  • the separator of the electrochemical device plays an important role of passing the electrolyte or the ions while isolating the cathode and the anode to prevent short circuit between the two electrodes.
  • the separator is required for various characteristics from an electrical, chemical and mechanical point of view.
  • the separator is firmly adhered to the electrode, and at the same time, it is required to have a sufficient mechanical strength even though it is thin for light weight and compactness of the electrochemical device.
  • Such a separator may be made of a polyolefin-based porous polymer substrate, but the porous polymer substrate has a problem in that electrolyte solution wettability is insufficient in comparison with an electrode. This problem also applies to the case where a porous coating layer including a mixture of inorganic particles and a binder polymer is formed on at least one surface of the porous polymer substrate, even if the electrolyte solution impregnation of the porous coating layer is improved. Because it does not.
  • the problem to be solved by the present invention is to provide a separator excellent in electrolyte solution impregnation of the porous polymer substrate while showing a strong adhesive force with the electrode.
  • Another problem to be solved by the present invention is to provide an electrochemical device that is improved by the battery life characteristics while the activation process time is shortened by including the separator.
  • a porous polymer substrate having a plurality of pores; And a layer formed from at least one surface of the porous polymer substrate formed from a binder polymer solution including a first binder polymer and a second binder polymer, wherein the horizontal axis is a frequency (rad / s) converted to a log scale.
  • the first binder polymer includes 30% by weight of methanol in a range of 0.01 to 10 rad / s.
  • the slope of the frequency-storage modulus curve is greater than 0 and less than or equal to 1.0 when added to the solvent at a concentration of 3% by weight, and the second binder polymer is added at a concentration of 3% by weight in a solvent containing 30% by weight of methanol.
  • a separator for an electrochemical device characterized in that the slope of the storage modulus curve is greater than 1.0 and less than 2.0.
  • the first binder polymer and the second binder polymer may be used in a weight ratio composition of 20: 1 to 2: 1.
  • Inorganic particles may be further included in the layer including the first binder polymer and the second binder polymer.
  • the inorganic particles may be inorganic particles having a dielectric constant of about 5 or more, inorganic particles having lithium ion transfer ability, or mixtures thereof.
  • the dielectric constant of about 5 or more inorganic particles are boehmite, BaTiO 3, Pb (Zr x Ti 1-x) O 3 (PZT, where, 0 ⁇ x ⁇ 1 Im), Pb 1 - x La x Zr 1 - y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), (1-x) PB (Mg 1/3 Nb 2/3 ) O 3 -xPbTiO 3 (PMN-PT, where 0 ⁇ x ⁇ 1), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 and SiC It may be any one or a mixture of two or more thereof.
  • the inorganic particles having a lithium ion transfer ability include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), and lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), (LiAlTiP) x O y series glass (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium germanium thiophosphate (Li x Ge y P z S w , 0 ⁇ x ⁇ 4 , 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ w ⁇ 5), lithium nitride (Li
  • (S1) preparing a porous polymer substrate having a plurality of pores; (S2) preparing a binder polymer solution including a first binder polymer and a second binder polymer, a solvent for dissolving both of the binder polymers, and a non-solvent not dissolving both of the binder polymers; And (S3) coating the binder polymer solution on at least one surface of the porous polymer substrate, and separating the phases under humidified conditions.
  • a method of manufacturing a separator for an electrochemical device is provided.
  • the solvent is acetone, dimethyl acetamide (DMAc), dimethyl formamide (DMF), tetrahydrofuran, tetrahydrofurane, methylene chloride (MC), chloroform, N It may be any one selected from the group consisting of -methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) and cyclohexane (cyclohexane) or a mixture of two or more thereof.
  • the non-solvent may be any one selected from the group consisting of methanol, ethanol, isopropyl alcohol, butanol, ethyl acetate and water, or a mixture of two or more thereof. have.
  • the weight ratio of the solvent and the non-solvent may be 98: 2 to 50:50.
  • the humidification condition may be a relative humidity of 40 to 80% at a temperature of 25 to 80 °C.
  • the separator prepared according to one aspect of the present invention can not only be firmly adhered to the electrode by the binder polymer distributed on the surface, but also the electrolyte impregnating property of the porous polymer substrate due to the binder polymer penetrated and coated on the porous polymer substrate. Has the effect of improving.
  • a separator includes a porous polymer substrate having a plurality of pores; And a layer formed from at least one surface of the porous polymer substrate formed from a binder polymer solution including a first binder polymer and a second binder polymer, wherein the horizontal axis is a frequency (rad / s) converted to a log scale.
  • the first binder polymer includes 30% by weight of methanol in a range of 0.01 to 10 rad / s.
  • the slope of the frequency-storage modulus curve is greater than 0 and less than or equal to 1.0 when added to the solvent at a concentration of 3% by weight, and the second binder polymer is added at a concentration of 3% by weight in a solvent containing 30% by weight of methanol.
  • the slope of the storage modulus curve is greater than 1.0 and less than 2.0.
  • the 'methanol' is used as a non-solvent for the binder polymer, the storage modulus of the binder polymer is greatly different depending on the type and content of the non-solvent.
  • solvent is a solvent for the binder polymer.
  • 'Storage modulus' refers to the amount of elastic energy accumulated in a vibrating sample, the slope of the storage modulus of the ideal binder polymer solution is 2, but the slope of the storage modulus when the phase separation occurs with respect to the non-solvent Tends to be lower.
  • the slope of storage modulus when 30% by weight of methanol is added to the solvent, when the slope of storage modulus is 1 or less, it is sensitive to humidifying phase separation, which is advantageous for forming an electrode adhesive layer, and when the slope of storage modulus is greater than 1, it is not sensitive to humidification phase separation.
  • the drying process it is possible to continuously move into the pores of the porous coating or the porous polymer substrate to improve the electrolyte impregnation characteristics.
  • the horizontal axis is the frequency (rad / s) of the binder polymer solution converted to log scale, and the vertical axis is the logarithmic binder polymer.
  • the frequency-storage modulus curve which is the storage modulus of solution (Pa)
  • the slope of the frequency-storage modulus curve of the ideal binder polymer solution is that the first binder polymer should exhibit fast phase separation behavior under humidified phase separation conditions. Theoretically, it is required to be greater than 0 and less than or equal to 1.0.
  • Non-limiting examples of such a first binder polymer include polyvinylidene fluoride (PVDF), PVdF-HFP, PVdF-HFP having a HFP substitution rate of 9% or less, a PVDF copolymer having a low degree of copolymer substitution, or a mixture thereof. Etc., but is not limited thereto.
  • the horizontal axis is the frequency (rad / s) of the binder polymer solution converted to the log scale
  • the vertical axis is the logarithmic binder polymer.
  • the slope of the frequency-storage modulus curve of the ideal binder polymer solution is that the second binder polymer should exhibit slow phase separation behavior under humidified phase separation conditions. In theory it is required to be greater than 1.0 and less than or equal to 2.0.
  • Non-limiting examples of such a second binder polymer is PVdF-HFP, PVdF-HFP, PVdF-CTFE, polyvinylacetate, cyanoethyl pullulan, cyanoethylpolypoly with 12% or more HFP substitution rate Vinyl alcohol (cyanoethyl polyvinylalcohol), PVDF having a high degree of copolymer substitution, or a mixture thereof, but is not limited thereto.
  • One of the ways to enhance the storage modulus is to enhance the storage modulus by adding a non-solvent.
  • the first binder polymer and the second binder polymer may be used in a weight ratio composition of 20: 1 to 2: 1.
  • the improvement of the electrolyte impregnation characteristics is insignificant, and when the first binder polymer is used less than the lower limit, phase separation may occur slowly, resulting in poor coating productivity and insufficient electrode adhesion of the separator.
  • the solvent that can be used in the present invention acetone (acetone), dimethyl acetamide (DMAc), dimethylformamide (dimethylformamide, DMF), tetrahydro furan (tetrahydro furan), methylene chloride (MC), It may be any one selected from the group consisting of chloroform, N-methyl-2-pyrrolidone (NMP) and cyclohexane, or a mixture of two or more thereof. It is not limited only to this.
  • the solvent may be removed in the manufacturing process of the electrochemical device, since the solvent may cause various side reactions when remaining in the finally manufactured electrochemical device.
  • the non-solvent may be any one selected from the group consisting of methanol, ethanol, isopropyl alcohol, butanol, ethyl acetate and water, or a mixture of two or more thereof. It is possible, but not limited to.
  • the mixing weight ratio may be 99: 1 to 40:60, or 98: 2 to 50:50, and when the mixing weight ratio range is satisfied, the binder polymer may be used in the porous polymer substrate. It can be permeated to form a coating.
  • the binder polymer solution according to the present invention may further include inorganic particles.
  • a porous coating layer in which the binder polymer and the inorganic particles are mixed may be formed on one or both surfaces of the porous polymer substrate.
  • the inorganic particles serve as a kind of spacer that can maintain the physical form of the porous coating layer, thereby suppressing thermal shrinkage of the porous polymer substrate when the electrochemical device is overheated, and the cathode and the anode even when the porous polymer substrate is damaged. To prevent direct contact.
  • such a porous coating layer may be prepared by coating a slurry including a solvent, a non-solvent, a binder polymer and inorganic particles by dip coating on a porous polymer substrate, and then drying.
  • the inorganic particles that can be used in the present invention is not particularly limited as long as it is electrochemically stable. That is, the inorganic particles that can be used in the present invention are not particularly limited as long as the oxidation and / or reduction reactions do not occur in the operating voltage range (for example, 0 to 5 V on the basis of Li / Li + ) of the applied electrochemical device.
  • the ionic conductivity of the electrolyte may be improved by contributing to an increase in the dissociation degree of the electrolyte salt such as lithium salt in the liquid electrolyte.
  • the inorganic particles may include high dielectric constant inorganic particles having a dielectric constant of 5 or more, or 10 or more.
  • inorganic particles having a dielectric constant of 5 or more include boehmite, BaTiO 3 , Pb (Zr x Ti 1-x ) O 3 (PZT, where 0 ⁇ x ⁇ 1), Pb 1 - x La x Zr 1 - y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), (1-x) Pb (Mg 1/3 Nb 2/3 ) O 3 -xPbTiO 3 (PMN-PT, where 0 ⁇ x ⁇ 1), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , SiC and
  • an inorganic particle having lithium ion transfer ability that is, an inorganic particle containing lithium element but having a function of transferring lithium ions without storing lithium
  • inorganic particles having a lithium ion transfer capacity include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2 -39P 2 (LiAlTiP) x O y series glasses such as O 5 (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3 , 0 ⁇ x ⁇ 2,
  • Lithium germanium thiophosphate such as Li x Ge y P z S w , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ w ⁇ 5), Li 3 N, etc.
  • SiS 2 series glasses Li x Si y S z , 0 ⁇ x ⁇ 3) such as Ride (Li x N y , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 2), Li 3 PO 4 -Li 2 S-SiS 2, etc.
  • LiI-Li 2 SP 2 S 5 P 2 S 5 series glass LiI-Li 2 SP 2 S 5 P 2 S 5 series glass (Li x P y S z , 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 7), or a mixture thereof.
  • the size of the inorganic particles is not limited, but for proper porosity of the separator, the average particle size may be in the range of 0.001 ⁇ m to 10 ⁇ m.
  • the composition ratio of the inorganic particles and the binder polymer in the porous coating layer may be, for example, about 50:50 to about 99: 1, or about 60:40 to about 95: 5.
  • the thickness of the porous coating layer composed of the inorganic particles and the binder polymer is not particularly limited, but may range from about 0.01 to about 20 ⁇ m.
  • the pore size and porosity are also not particularly limited, but the pore size may range from about 0.01 to about 5 ⁇ m, and the porosity may range from about 5 to about 75%.
  • the component of the porous coating layer in addition to the inorganic particles and the binder polymer described above, other additives commonly used in the art may be further included.
  • the binder polymer is attached to each other (that is, the binder polymer is connected and fixed between the inorganic particles) so that the inorganic particles are bound to each other, and the porous coating layer is formed of the porous polymer substrate by the binder polymer. It remains bound with.
  • the interstitial volume between the inorganic particles which is a space defined by the inorganic particles that are substantially interviewed, becomes the pores of the porous coating layer. .
  • the porous polymer substrate may be used as long as it is a porous polymer substrate commonly used in an electrochemical device.
  • a polyolefin-based porous membrane or a nonwoven fabric may be used, but is not particularly limited thereto.
  • Non-limiting examples of the polyolefin-based porous membrane polyolefin-based porous membrane, polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof And a membrane formed of a polymer.
  • the nonwoven fabric may be, for example, polyethylene terephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, polycarbonate, or polycarbonate. ), Polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfide, polyethylenenaphthalene, etc. Or the nonwoven fabric formed from the polymer which mixed these is mentioned.
  • the structure of the nonwoven can be a spunbond nonwoven or melt blown nonwoven composed of long fibers.
  • the thickness of the porous polymer substrate is not particularly limited, but may be 5 to 50 ⁇ m, and the pore size and pore present in the porous polymer substrate are also not particularly limited, but may be 0.01 to 50 ⁇ m and 10 to 95%, respectively.
  • the method of coating the solution containing the binder polymer or the slurry containing the binder polymer and the inorganic particles on the porous polymer substrate may use a conventional coating method known in the art, for example, dip coating, Various methods may be used, such as die coating, roll coating, comma coating, or a mixture thereof.
  • the slurry may be selectively coated on both surfaces or only one surface of the porous polymer substrate.
  • the coating process can be carried out in a range of relative humidity, preferably at a temperature of 25 to 80 °C under a relative humidity of 40 to 80%.
  • a temperature during the coating process is lower than the lower limit, drying of the porous coating layer is slow, and when the temperature is higher than the upper limit, the time required for phase separation of the binder polymer may be insufficient.
  • the relative humidity in the coating process is lower than the lower limit, the amount of moisture, which is a non-solvent introduced during the vapor-induced phase separation, is difficult to separate the phase, and when the relative humidity is higher than the upper limit, moisture is condensed in the drying furnace. Problems will arise.
  • the first binder polymer and the second binder polymer dissolved in the solution / slurry during the drying process have different phase transition characteristics by humidifying phase separation phenomenon known in the art.
  • Binder polymers having a slope of the frequency-storage modulus curve greater than 1.0 and less than or equal to 2.0 have a slow phase separation rate under the same nonsolvent, and require a relatively large amount of nonsolvent required for phase separation.
  • it may exist in the first half of the thickness direction of the porous coating layer after coating or penetrate into the porous polymer substrate.
  • the binder polymer which makes the slope of the frequency-storage modulus curve greater than 0 and equal to or less than 1.0 has a high phase separation speed, requires a small amount of nonsolvent required for phase separation, and concentrates on the separator surface. Therefore, according to one embodiment of the present invention, some of the binder polymers are intensively distributed on the surface of the separator and exhibit excellent adhesion with the electrode, while the other binder polymer penetrates into the porous polymer substrate to form a coating and has an excellent electrolyte solution of the porous polymer substrate. Show impregnation.
  • the drying process carried out subsequently may be carried out by methods known in the art and may be batchwise or continuously using an oven or heated chamber in a temperature range that takes into account the vapor pressure of the solvent used.
  • the drying is to almost eliminate the solvent present in the slurry, which is preferably as fast as possible in view of productivity and the like, for example, may be carried out for a time of 1 minute or less, preferably 30 seconds or less.
  • an electrochemical device includes a cathode, an anode, and a separator interposed between the cathode and the anode, wherein the separator is the separator of the present invention described above.
  • the electrochemical device includes all devices that undergo an electrochemical reaction, and specific examples include capacitors such as all kinds of primary, secondary, fuel cell, solar cell, or super capacitor devices. capacitor).
  • capacitors such as all kinds of primary, secondary, fuel cell, solar cell, or super capacitor devices. capacitor).
  • a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery among the secondary batteries is preferable.
  • the electrode to be applied to the electrochemical device according to an embodiment of the present invention is not particularly limited, and according to a conventional method known in the art, the electrode active material may be manufactured in a form bound to the electrode current collector.
  • Non-limiting examples of the cathode active material of the electrode active material may be a conventional cathode active material that can be used for the cathode of the conventional electrochemical device, in particular lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide or a combination thereof One lithium composite oxide can be used.
  • Non-limiting examples of the anode active material may be a conventional anode active material that can be used in the anode of the conventional electrochemical device, in particular lithium metal or lithium alloys, carbon, petroleum coke, activated carbon, Lithium adsorption materials such as graphite or other carbons are preferable.
  • Non-limiting examples of the cathode current collector is a foil made by aluminum, nickel or a combination thereof, and non-limiting examples of the anode current collector by copper, gold, nickel or a copper alloy or a combination thereof. Foils produced.
  • the electrolyte salt included in the nonaqueous electrolyte solution which can be used in one embodiment of the present invention is a lithium salt.
  • the lithium salt may be used without limitation those conventionally used in the lithium secondary battery electrolyte.
  • For example is the above lithium salt anion F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 - , (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, ( CF 3 SO 2) 3 C -
  • organic solvent included in the non-aqueous electrolyte solution those conventionally used in the lithium secondary battery electrolyte solution can be used without limitation.
  • ethers, esters, amides, linear carbonates, cyclic carbonates, and the like can be used alone or in combination of two or more. It can be mixed and used.
  • carbonate compounds which are typically cyclic carbonates, linear carbonates, or mixtures thereof may be included.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate and any one selected from the group consisting of halides thereof or mixtures of two or more thereof.
  • halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
  • linear carbonate compounds include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • EMC ethylmethyl carbonate
  • methylpropyl carbonate and ethylpropyl carbonate methylpropyl carbonate and ethylpropyl carbonate.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are high viscosity organic solvents and have a high dielectric constant, which may dissociate lithium salts in the electrolyte more effectively.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are high viscosity organic solvents and have a high dielectric constant, which may dissociate lithium salts in the electrolyte more effectively.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether, or a mixture of two or more thereof may be used. It is not limited.
  • Ester in the organic solvent is methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone and ⁇ Any one or a mixture of two or more selected from the group consisting of caprolactone may be used, but is not limited thereto.
  • the injection of the nonaqueous electrolyte may be performed at an appropriate step in the manufacturing process of the electrochemical device, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the electrochemical device assembly or the final step of the electrochemical device assembly.
  • the electrochemical device according to the present invention in addition to the winding (winding) which is a general process, the lamination (stacking) and folding (folding) process of the separator and the electrode is possible.
  • the external shape of the electrochemical device is not particularly limited, but may be cylindrical, square, pouch or coin type using a can.
  • the slurry was coated on both sides of a polyethylene porous membrane (ND307B, Asahi Co., Ltd.) having a thickness of 7 ⁇ m by dip coating to form a porous coating layer.
  • the thickness of the porous coating layer was adjusted to about 4 ⁇ m.
  • a separator was prepared in the same manner as in Example 1, except that 3.3 parts by weight of polyvinylidene fluoride (LBG, Arkema, HFP content 5%) was used alone.
  • a separator was prepared in the same manner as in Example 1, except that 1.0 parts by weight of an acrylic copolymer (CSB130, Toyo ink Co., Ltd.), a particulate water-dispersible emulsion binder polymer, was used as the binder polymer and water was used as the solvent.
  • CSB130 acrylic copolymer
  • Toyo ink Co., Ltd. a particulate water-dispersible emulsion binder polymer

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Abstract

La présente invention se rapporte à un séparateur pour un élément électrochimique présentant une meilleure mouillabilité d'électrolyte et à un élément électrochimique comprenant le séparateur. Une couche contenant au moins deux polymères liants présentant des pentes différentes sur la courbe de module élastique de stockage de fréquence est formée sur une surface du séparateur, et, dans ce cas, l'un des polymères liants est réparti de manière concentrée sur la surface du séparateur, ce qui permet d'obtenir une forte adhérence entre le séparateur et l'électrode, et l'autre polymère liant se répand dans un substrat polymère poreux et recouvre ce dernier, ce qui permet d'améliorer la mouillabilité d'électrolyte.
PCT/KR2016/004522 2015-04-30 2016-04-29 Séparateur pour un élément électrochimique présentant une meilleure mouillabilité d'électrolyte et élément électrochimique comprenant ce même séparateur WO2016175605A1 (fr)

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CN110249447A (zh) * 2017-02-13 2019-09-17 株式会社Lg化学 包括粘合剂层的锂二次电池隔板
CN110350129A (zh) * 2019-07-09 2019-10-18 东华理工大学 一种具有电化学活性的锂离子电池复合隔膜及制备方法和应用
CN112106223A (zh) * 2018-07-13 2020-12-18 株式会社Lg化学 包含低电阻涂层的电化学装置用隔膜和制造所述隔膜的方法
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CN110249447A (zh) * 2017-02-13 2019-09-17 株式会社Lg化学 包括粘合剂层的锂二次电池隔板
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CN112106223A (zh) * 2018-07-13 2020-12-18 株式会社Lg化学 包含低电阻涂层的电化学装置用隔膜和制造所述隔膜的方法
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CN110350129B (zh) * 2019-07-09 2022-05-06 东华理工大学 一种具有电化学活性的锂离子电池复合隔膜及制备方法
CN114641893A (zh) * 2019-12-20 2022-06-17 株式会社Lg新能源 隔板、包括隔板的锂二次电池及其制造方法
CN113823877A (zh) * 2021-08-31 2021-12-21 远景动力技术(江苏)有限公司 锂离子电池的隔膜及其制备方法和用途

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